Process for breaking petroleum emulsions



Patented Feb. 20, 1951 PROCESS FOR/BREAKING PETROLEUM EMULSIONS Melvin De Grootc, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application December 13, 1948, Serial No. 65,088

11 Claims.

This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-in-oil seam type, and particularly petroleum emulsions.

This invention is a continuation-in-part of our co-pending application Serial No. 726,209, filed February 3, 1947' (now abandonedk See our copending applications Serial No. 8,731, filed February 16, 1948 (now abandoned), and also Serial No. 82,704, filed March 21, 1949 (now Patent No. 2,499,370 granted March 7, 1950). Attention is also directed to our co-pending application Serial No. 65,086, filed December 13, 1948.

Complementary to the above aspect of the invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical'compounds, products, and the like, in various other arts and industries, along with the methods for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. Serial No. 65,089, filed December 13, 1948.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as "cut oil, "roily oil, emusified oil, etc., and which comprise fine droplets of naturally-occurring waters or'brines dispersed in.

: thetic products.

See our co-pending application a more or less permanent state throughout the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion in the absence of such precautionary measure. larly, such demulsifier may be mixed with the hydrocarbon component.

Simi- 2 i. .n/ Briefly stated, the present process is concerned with the breaking or resolving of petroleum emusions by means of quaternary ammonium compounds obtained from certain esters which are, in turn, derivatives of specific synthe oxyalkylated derivatives of certain resins hereinafter specified.

Thus, the present process is concerned with breaking petroleum emulsions of the water-inoil type, characterized by subjecting the emulsion to the specific hydrophile quaternary ammonium compounds hereinafter described. Said hydrophile quaternary ammonium compounds are obtained by reaction between a hydroxylated high molal amine selected from the class consisting of and R20) "H RN n in which R is an alkyl radical having at least 8 and not more than 26 carbon atoms; R1 is an alkyl radical having not over 26 carbon atoms; R20 is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, butylene oxide, glycide, and methylglycide radicals; n represents the numeral 1 to 6, and n" represents the numeral 1 to 3; and the ester of an alphahalogen monocarboxylic acid having not over 6 carbon atoms and hydrophile hydroxylated synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide; and (B) an oxyalkylation susceptible, fusible, organic solvent-soluble, water-insoluble, phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and NOV 2? 1 b These products are, in turn,

an aldehyde having not over 8 carbon atoms and reactive towards said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula:

in which R4 is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkyl- '15 ated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having theformula '(R3'O).n,'i'n which R3 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 20, with the proviso that at least 2 moles of a'lkylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of the ultimate quaternary ammonium compound as .Well as the oxyalkylated resin in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. For convenience, what is said hereinaftermay be divided into five parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; Part 3 will be concerned with the conversion of the immediately aforementioned derivative into a total'or partial ester by reaction with chloroacetic acid, or the like; Part 4 will be concerned with a reaction between such esters containing a labile halogen and the hydroxylated high molal amines of the kind previously dscribed'; and Part 5 will be concerned with the use of such quaternary ammonium compounds as demulsifiers, as hereinafter described.

4 ylphenol. In the instant invention it may be first suitable to describe the alkylene oxides employed as reactants, then the aldehydes, and finally the phenols, for the reason that the latter require a more elaborate description.

The alkylene oxides which may be used are the alpha-beta oxides having not more than 4 carbon atoms, to Wit, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glycide, and methylglycide.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of formaldehyde are more "expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difficulties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinification when treated with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a r sin. This is illustrated, for example, by the different characteristics of the resin prepared from para-tertiary amylphenol and formaldehyde on on hand, and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas the latter is soft and tacky,-and obviously easi-r to handle in thesubsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde.

' "quires careful control for the reason that in addi- The employment of furfural retion to its aldehydic function,furfural can form vinylcondensations by virtue of its unsaturated structure. The production of resins from furfural-for use in preparing reactants for the pres- PARTl R R n" R In such idealized representation 11'' is a numeral varying from 1 to 13 or even more, provided that the resin is fusible and organic solvent-soluble. R. is a hydrocarbon radical having at least 4 and notover 8 carbon atoms. In the instant application R may have as many as 12 carbon atoms, as ;;in the case of a resin obtained, from a dodec-.

' 'ent process is'most conveniently conducted with Weak alkaline catalysts and often with alkali metal-carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, 2-ethylhexanal, ethyl-- butyraldehyde, heptald'ehyde, and benzaldehyde, It would appear that the' furfural and glyoxal. use of glyoxal should be avoided. due to the fact that it is tetrafunctio'nal. However, our experience has been that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resi'ni fication reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say,

one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which are used as intermediates in this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases.

It is generally accepted that when ammonia and amines are I employed as .catalysts theyenter into thecondensation reaction and, inlfact, may operate byv initial'combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes diiiicult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between the use of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where diiferent basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc. r

Suitable phenolic reactants include the following: Para-tertiarybutylphenol; para-secondarybutylphenol; para-tertiary-amylphenol; parasecondary-amylphenol; para-tertiary-hexylphenol; para-isooctylphenol; ortho-phenylphenol; para-phenylphenol; ortho-benzylphenol; parabenzylphenol; and para-cyclohexylphenol, and the corresponding ortho-para substituted metacresols and 3,5-xylenols. Similarly, one may use paraor ortho-nonylphenol or a mixture, paraor ortho-decylphenol or a mixture, menthylphenol, or paraor ortho-dodecylphenol.

For convenience, the phenol has previously been referred to as monocyclic in order to differentiate from fused nucleus polycyclic phenols, such as substituted naphthols. Specifically, monocyclic is limited to the nucleus in which the hydroxyl radical is attached. Broadly speaking, where a substituent is cyclic, particularly aryl, obviously in the usual sense such phenol is actually polycyclic although the phenolic hydroxyl is not attached to a fused polycyclic nucleus. Stated another way, phenols in which the hydroxyl group is directly attached to a condensed or fused polycyclic structure, are excluded. This matter, however, is clarified by the following consideration. The phenols herein contemplated for reaction may be indicated by the following formula:

in which R is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that one occurrence of R is the hydrocarbon substituent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of the 3 and 5 positions may be methyl substituted.

The above formula possibly can be restated more conveniently in the following manner, to wit, that the phenol employed is of the following formula, with the proviso that R is a hydrocarbon substituent located in the 2,4,6 position, again with the provision as to 3 or 3,5 methyl substitution. This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

The manufacture of thermoplastic phenol aldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted by a hydrocarbon group, and particularly by one having at least 4 carbon atoms and not more than 12 carbon atoms, is well known. As has been previously pointed out, there is no objection to a methyl radical provided it is present in the 3 or 5 position.

Thermoplastic or fusible phenol-aldehyde resins are usually manufactured for the varnish trade and oil solubility is of prime importance. For this reason, the common reactants employed are butylated phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difliculty, while when a water-insoluble phenol is employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In such cases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfa-acid. Addition of a solvent such as xylene is advantageous as hereinafter described in detail. Another variation of procedure is to employ such organic sulfo-acids, in the form of their salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or sufficient, at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant can be distilled off and thus recovered from,

amaooa w thtreactionmass. This same procedure may be used'with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of oneto-"one or thereabouts. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much as two moles of formaldehyde, for example, per mole of phenol, or even more, with the result that only a small part of such aldehyde remains uncombined or is subsequently liberated during resinification. Structures which have been advanced to explain such increased use of aldehydes are the following:

OH OH Such structures may lead to the production of cyclic polymers instead of linear polymers. For this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structui'es.

Sometimes conventional resinification procedure is employed using either acid or alkaline catalysts to produce low-stage resins. Such resins may be employed as such, or may be altered or converted into high-stage resins, or in any event, into resins of higher molecular weight, by heatingalong'with the employment of vacuum so as to split off water of formaldehyde, or both. Generally speaking, temperatures employed, particularlywith vacuum, may be in the neighborhood of 17 to 250 'C., or thereabouts.

It may be'well to point out, however, that the amount of formaldehyde used may and does usually affect the length of the. resin chain. Increasing the amount of the aldehyde, such as formaldehyde, usually increases the size or molecular weight of the polymer.

-In the'hereto appended claims there is specified, among other things, the resin polymer containing at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resins. As a matter of fact, using the procedures herein described or any conventional resinification procedure will yield products usually having definitely in excess of 3 nuclei. In other words, a resin having an average of 4, 5 035 /2 nuclei per unit is apt to be formed as a minimum in resinification, except under certain special conditions where dimerization may occur.

, However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, ,etc., or some other suitable solvent which boilsor refluxes at a higher temperature,-instead of xylene, in subsequent examples, and ifon'ef doubles or triples the amount of catalyst, 'doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly The molecular weight determinations, of course, require that the product be completely. soluble in the particular solvent selected as, for The molecular weight determination of such solution may involve either the instance, benzene.

freezing point asin the cryoscopic method, or,less

conveniently perhaps, the boiling point in an e'bul- -liosc'opic method. The advantage of the ebullioscopic method is that, in comparisonwith the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ 1 is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for dc termining the molecular weights of resins, es-

pecially solvent-soluble resins, is the cryosc'opic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co., 1947).

Subsequent examples will illustrate the use of an acid catalyst, an alkaline. catalyst, and no As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfo-acid catalyst.

and a mineral acid, along with a suitable solvent,

;,such as xylene, as hereinafter illustrated in de- However, We have obtained products from tion of both types of catalysts is used in different stages of resinification. Resins soobtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as highstage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. Fo' instance, acid catalyzed resins obtained in the usual manner and having a molecular weight indicating the presence of approximately 4 phenolic units or thereabouts maybe subjected to such treatment, with the result that,

one obtains a resin having approximately double this molecular weight. The usual procedure isto use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinification employing phenols of the kind here described, there is little or no tendency to form binuclear compounds, i. e., di-

mers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde, particularly .where the substituent has 4 or 5 carbon atoms. Where the number of carbon atoms in a substituent approximates the upper limit specified herein, there Sometimes the expression low- Although such may be some tendency to dimerization. The usual procedure to obtain a dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from substituted phenols are not resins as that term is used herein.

Although any conventional procedure ordinarily employed may be used in the manufacture of the herein contemplated resins or, for

that matter, such resins may be purchased in the open market, we have found it particularly desirable to use the procedures described elsewhere herein, and employing a combination of an organic sulfoacid and a mineral acid as a catalyst,

and xylene as a solvent. By way of illustration, certain subsequent examples are included, but it is to be understood the herein described invention is not concerned with the resins per se or with any particular method of manufacture but is concerned with the use of reactants obtained by the subsequent oxyalkylation thereof.

The phenol-aldehyde resins may be prepared in any suitable mann-r.

oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact betweena non-gaseous phase and a gaseous phase.

It can, for example, be carrLd out by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or

by treating a suitable solution or suspension. Since the m lting points of the resins are often higher than desired in the initial stage of oxyethylation, we have found it advantageous to use a solution or suspension of thermoplastic resin in an inert solvent such as xylene Under such circumstances, the resin obtained in the usual manner is dissolved by h-ating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during oxyalkylation, it is obvious there is no objection to having a solvent present during, the resinifying stage if, in addition to being inert towards the resin, it is also inert towards the reactants and also inert towards water. Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propyl benzene, mesitylene, decalin (decahydronaphthalene), tetralin (tetrahydronaphthalene), ethylene glycol diethylether, diethyl ne glycol diethylether, and 'tetraethylene glycol dimethylether, or mixtures of one or more. Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorine atom. in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable solvents may be s lected from this group A for molecular weight determinations.

The use of suchsolventsis a convenient expedient in the manufacture of the thermoplastic resins, particularly since the solv;nt gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary product of commerce containing about 37 /296 to 40% formaldehyde, is the preferred reactant. When such ls v n is used is .used .it is advanta eously added 10 at the beginning of the resinification procedure or before the reaction has proceeded very far.

The solvent can be removed afterwards by distillation with or Without the use of vacuum, and a final higher temperature can be employed to complete reaction if desired. In many instances it is most desirable to permit part of the solvent, particularly when it is inexpensive, e. g., xylene. to remain behind in a pred-termined amount so as to have a resin which can be handled more conveniently in the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed, xylene or other inexpcnsive solvent may be added after the removal of decalin, if desired.

In preparing resins from difunctional phenols it is common to employ'reactants of technical The substituted phenols herein contemplated are usually derived from hydroxybenzene. As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequently in the neighborhood of 1/10 of 1%, or even less. The amount of the usual trifunctional phenol, such as hydroxybenzene or metacresol, which can be tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must not be sufficient to cause insolubility at the completion of the resinification stage or the lack of hydrophile properties at the completion of the oxyalkylation stage.

The exclusion of such trifunctional phenols as hydroxybenzene or metacresol is not based on the fact that the mere random or occasional inclusion of an unsubstituted phenyl nucleus in the resin molecule or in one of several molecules, for example, markedly alters the characteristics of the oxyalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxymethylol or a substituted hydroxymethylol group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insoluble resins or to nonhydrophilic products resulting from the oxyalkylation procedure. With this rationale understood, it is obvious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent that insolubility is produced in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly What is said hereafter in differentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organic solvent-soluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly if a resin prepared in the usual manner is converted into a higher stage resin by heat treatment in vacuum as previously mentioned. This again is a reason for avoiding any opportunity for cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant maycause cross-linking in a conventional resinification procedure, or in the oxyalkylation procedure, or in the heat and vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing intermediates to be used in practicing the invention is to prepare a resin employing formaldehyde in excess (1.2

III

molesof formaldehyde per mole of phenol)! and usingan acid catalystin the manner'descrihad in Example la. of our Patent. 2,4993% granted I- March 7, 1950. vent-soluble in any one of the aromatic or other solvents previously. referred to, it is then subjected to oxyethylation. During oxyeth-ylati'on a temperature is employed of approximately -'15Of"t0 165 C. with addition of at least 2 and advantageously up to 5 moles of ethylene oxide per phenolic hydroxyl. advantageously conducted. so. as to require from a few minutes up to 5 to 10 hours; so: obtained issolvent-soluble and self-dispersing 'oremulsifiable, or has emulsifying properties; the. phenol is. perfectly. satisfactory from the standpointiofi'trifunctional phenol content. The solventmaybe removed prior to theidispersibility 11.01 emulsifiability test. When a: product: becomes Jrubbcry duringoxyalkylation due to: the presence; of -a small'amount: of trireactiye phenol, as prev-iously mentioned, or forsome other reason, it may: become extremely insoluble, and no longer .'qualifies as being. hydrophile. as hereinspecifi'ed. Increasing-the size of the; aldehydic'nucleus, forz'. 2' instance using heptald'ehyde instead. of formaldehyde; I phenoL.

If ithe resin so obtained is sol- The oxyethylation is If the product increases tolerance for triiunctional The presence of a trifunctional or tetrafunc- *tional phenol (such as resorcinol or bisphenol A) is apt to produce detectable cross-linking and in- This of conventional resin manufacture, the proceduresemploying difunctionalv phenolsare very apt-to; and almost invariably do, yield solventsoluble, fusible resins. vtional. procedures are employed in connection with resins for varnish manufacture; or. the like, there is involved the matter of color, solubility inxoil, etc.

However, when conven- When resins of the same type are manufactured. for the herein contemplated purpose, i. e.,. as. a raw material to be subjected; to

' oxyalkylation', such criteria of selection are no longer pertinent;

Stated; another, way, one may use more drastic conditions. of resinificati'on than thosev ordinarily employed'to produce resins for the present purposes. Such more drastic conditions. of resiniflcation may include increased amounts. of catalyst, higher temperatures, longer time -of reaction, subsequent-reaction involving heat alone. or in-combinationpwith.vacuum; etc.

Therefore, one is' not only concerned with. the resinification reactions which yield the bulk of ordinary'resins from difunctional, phenols but- I also and. particularly with the minor reactions of ordinary resin manufacturewhich are of importance inthepresent invention forv the reason thatrthey'occuriunder more drastic conditions'of resinificationwhich maybe employed advantageously at times, and they" may lead to; crosslinking.

In this connection it may be well to. point'out that part of these reactions are now understood .or explainable. tea. greater. or lesser. degree in,

light of-ja mostrecent investigation. Reference is made-to the researches of Zinke and his: 00- workers, Hultzsch and his associates, and tovon Eulen and his co-workers; and others. As to a bibliography of such investigations, see Carswell, Phenoplasts, chapter 2. These investigators limited much of their'work to reactions involving phenols. having two. or less reactive hydrogen atoms; Much of what appears in these most recent and most up-to-date investigations is pertinentt'o thepresent. inventionv insofar that much of itiisreferring to resinificationinvolvingdifunctional phenols- For the: moment, it may besimpler to consider a-z1nosttypicaltype? ofgfusible resin andforget for the time that such resin, atleast underv certain-circumstances, is susceptible to further complications. Subsequently inthe text it will be pointed out that cross-linking or reaction with excess: formaldehyde maytake place; even with one of. such most typical type. resins. This point. is-made for-the reason that insolubles must be, avoided in. order to obtain the products herein contemplated for use as reactants.

The typical type of fusible resin obtained from. a para-biockedor ortho-blocked: phenol is clearly differentiated from theNovolak type or resole type of resin. Unlike the resole type, such typical type para-blocked or. ortho-blocked phenol resin may be heated indefinitely without passing into. an infusible stage, and in this respect is similar to a Novolak. Unlike the Novolak type the addition of a further reactant, for instancemore-aldehyde, does not ordinarily alter fusibility of the difunctional phenol-aldehyde typeresin; but such addition to a .Novolak causes cross-linking by virtue of the. available third functional position.

Whatv has been said. immediately preceding is subject to modification in this respect: It is well known, for example, that difunctional phenols, for instance; paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-hardenable resins, at least under certain conditions, as for example the use of two moles of formaldehyde to one of phenol, along with an alkaline catalyst. This peculiar hardening or curing or cross-linking of resins obtained from difunctional phenols has been recognized by formation of insolublesduring resin manufacture V ployed. orin theoxyalkylation procedure.

orthe subsequent stage of. resinmanufacture where heat alone, or heat and vacuum, are.-em-

In its simplest presentation the rationale of resinification involving formaldehyde, for example, anda difn'nctional; phenol would. not. be expected to form cross-links. However, crosselinking sometimes occursrand it may reach'the objectionable stage, Howeven provided that thepreparation of resins simply takes into cognizance the pres- .ent knowledge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest difficulty preparing a very large number of resins of; varioustypes and from variousreactantsand 70 by meansrof differentcatalysts by-difierent procedures, all. of. which are eminently suitable for the. herein described purpose.

Now returning to the thought that crosslinking can take place, even when difunctional phenolsare usedexclusively, attention is directed to the following: Somewhere during the course a of resin manufacture there may be a potential cross-linking combination formed but actual cross-linking may not take place until the subsequent stage is reached, 1. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related rexplained in terms of a theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that a CHzOH radical and H atom may not lie in the same plane in the manufacture of ordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolubles may be related to the aldehyde used and the ratio of aldehyde, particularly form-.

aldehyde, insofar that a sight variation may, under circumstances not understandable, produce insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity of formaldehyde employed and a slight increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. lhe cause of insoluble resin formation is not clear, and nothing is known as to the structure of these resins.

All that has been said previously herein as regards resinification has avoided the specific reference to activity of a methylene hydrogen atom. Actually there is a possibi ity that under some drastic conditions cross-linking may take place through formaldehyde addition to the methylene bridge, or some other reaction involving a methylene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily reactive,

possibly at times methy ol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, forinstance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solvent-soluble, particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility and solubi ity. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactan s, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distingu shed from Novolaks or resoles. When these resins are produced from difunctional phenos and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparative- W fluid at 110 to 165 C. as a rule and thus can be readily oxyalkylated. preferably oxyethylated, without the use of a solvent.

' Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified. as one which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it is obvious that a resin to be suitable need only be sufficiently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously described. Thus resins which are, strictly speaking, fusible but not necessarily thermoplastic in the most rigid sense that such terminology would be applied to the mechanical properties of a resin, are useful intermediates. The bulk of all fusible resins of the kind herein described are thermoplastic.

The fusible or thermoplastic resins, or solventsoluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydrophile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble is used to point out this characteristic of the resins used.

In the manufacture of compounds herein employed, particularly for demulsification, it is obvious that the res ns can be obtained by one of a number of procedures. In the first place, suitable resins are marketed by a number of companies and can be purchased in the open market; in the second place, there are a wealth of examples of suitable resins described in the literature. The third procedure is to follow the directions of the present application.

The polyhydric reactants, i. e., the oxyalkylation-susceptible, water-insoluble, organic solvent-soluble, fusible, phenol-aldehyde resins derived from difunctional phenols, used as intermediates to produce the products used in accordance with the invention, are exemplified by Examples Nos. 1a through 103a of our Patent 2,499,- 370, granted March '7, 1950, and reference is made to that patent for examples of the oxyalkylated resins used as intermediates.

Previous reference has been made tothe use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of parabuty phenol and para-amylphenol, or a mixture of para-butvlphenol and para-hexylphenol, or para-butylphenol and para-phenoylphenol. It is extremely dimcult to depict the structure of a resin derived from a single phenol. When mixtures of phenols are used, even in equimolar proportions, the structure of the resin is even more indeierminable. In other words, a mixture involving para-butylphenol and para-amylphenol might have an alternation of the two nuclei or one might have a series of butylated nuclei and then a series of amy ated nuclei. If a mixture of aldehydes is em loyed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more comp icated and possibly depends on the relative reactivity of the aldehydes. For that matter. one might be producing simultaneously two different resins, in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the oxyalkylated derivatives of such resins, de rived from such plurality of reactants, instead of l heing limited to; a single reactant from each: of thethree classes, is contemplated; and here included forthe reasonthat they are obvious variants.

PART. 2

Having obtained a suitable resin of the kind described, such resin is subjected totreatment with alowmolal reactive alpha-beta olefin oxide so asto render the product distinctly hydrophile in nature as indicated by the fact that it becomes .self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties. lhe olefin oxides employed are characterized; by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of, ethylene oxide, propylene oxide, .butylene oxide, glycide, and methylglycide.

Glycide may be, of course, considered as a,

.hydroxy propylene oxide and methyl glycide as ahydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered asderivatives of or substituted ethylene oxides. .Thesolubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2 In glycide, it is 2:3; and in methyl glycide, 1:2. In suchcompounds, the ratio is very favorable to the production of hydrophile or surf-aceacti ve properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily. employed only where the resin composition is such as to make incorporation of the de- .sired, property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are .usable in conjunction with the three more favorable alkyleneoxides in all cases. For instance, latter one or several propylene oxide or butylene oxide molecules. have been attached to the resin molecule, oxy-alkylation may be satsfactorily continued using the more favorable members of the. class, to produce the desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficienty hydrophile derivatives because of their relatively oxygen-carbon ratios.

Thus, ethylene oxide ismuch more effective than propylene oxide, and propylene oxide is -more effective than butylene oxide. Hydroxy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl' glycide) is more eiiective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available'and is reactive, itsuseis definitely advantageous, and especially -inlight of itshigh Oxygen content. Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glyc'de -may react with a most explosive violence and must be handled with extreme care.

The, oxyalkylation of resins of the kind from which the initial reactants used in the practice .of. the present invention are prepared is advantageously catalyzed by the presence of an alkali. -Usefu1 I alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The immeratu eemplcy d m y. vary fromroom temlow perature to ashigh, as: 200- C; Thereaction; may be conducted with or without pressure,- i. e., from zero pressure to approximately 200 or even300 pounds gauge pressure (pounds per square inch). In a general way, the method employedissuh stant'ally the same procedure as used, for

oxyalkylation of other organic materials having reactive phenolic groups,

It may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as-sulfuric acid is used to catalyze the resinific-ation reaction, presumably after being converted into a sulfonic acid, it may be necessary and; is usually advantageous to addan amount of alkali equal stoichiometrically to such acidity, and-include added alkali. over and above this amount as the alkaline catalyst.

It isadvantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins, theoxyalkylation proceeds sat'sfactorily without a solvent. Since xylene is cheap and may be permitted to be: present in theyfinal product. used as a demulsifier, it isour preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including '7' units permolecule.

If a xylene solution is usedin an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also duepto ethylene oxide or whatever other oxyalkylating agent is used. Undersuch circumstances it may be necessary at times to use substantial pressures to obtain effective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of approximatel 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in thehardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be reacted further in i the usual manner with ethylene oxide or som other suitable reactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent'by distillation in the customary manner.

- Another suitable procedure is to use propylene oxide or-butylene oxide as a solvent as well as-a reactant in the earlier-stages along with ethylene oxide, for instance, bydissolving the powdered resin in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene oxide orbutylene oxide, or a mixture which includes the oxyalkylatecl product, ethylene oxide is added to react with the liquid mass until hydrophile' propertiesare obtained. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final'product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation. in any suitable manner.

Attention is directed to the fact thatthe resins herein described must be fusible or soluble in an organic solvent. Fusible resins invariably are soluble in "one or more organic solventssuclras those mentioned elsewhere herein: is to be emphasized, however, that the organic solvent emplayed to indicate or assure that the resin meets this requirement need not be" oneused in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such sol vents are alcohols and alcohol-thers. However, where aresin is soluble in an organic solvent, there are usually available other organic solvents which are not susceptible tooxyalkylatio'n, useful for the oxyalkylatiori step. In any event, the 'or-= and the quantitative nature of'the'esterification itself, i. e.,' whether it is total or partial, and also by the hydr oxylated highm'olal'amineu'sed' to h obtain the final product ior'use in the process of the present invention. It may be well, however, topoint out what has beensaid elsewhere in regard to the hydroxylated intermediate reactants.

See, for example, our co-pen'ding applications,

Serial NOS. 8,730 and 8,731; both filed. February 16, 1948, and Serial NO. 42,133, filed August" 2, 1948, and .SerialNo. 42,134, filed August 2, 19.48 (all "four cases now abandoned). The reason is thatthe reactiOna'depending on the acid and the hydroxylated high molal amine selected, may vary the hydrophile-hydrophobe balance in one direction orthe other, and also inyariablycauses the development ofsome propert whichmakes it inherently difierent from the reactants from which the derivative is obtained.

Referring td the .hydrophile hydroxylated intermediates, even more remarkable and equally difiicult to explain, are the versatility andthe utility of these compounds considered as chemical reactants as one goes from ininimum hydrophile property to ultimate maximumhydrophile property. For instance, minimum' hydrophile property may be described roughlyas the point where two ethyleneoxy radicals or moderately in excess'thereof are introduced perphenolic'hydroxyl; Such minimum hydrophile'property'or sub-surface-activity or minimum surface-activity means that the product shows at least emulsifying properties orself-disisersiod cold' or even in warm distilled w'ate1'(15 to 40 'C.) in concentrations of 015% to5.0%. These materials are generally more soluble in cold water than warm water, and ma even be very insoluble in boiling water. Moderately hightemperatiires aid in reducing the viscosity oith'e'sdlute underexa imation. Sometimes if one continues to shake hot solutiom even thoughploudyor containing n. o uhleph eo e, fi s that i j e take 91? to s eia omqse sbu she mi e Suchproperties in turn, of course, are effected subse- 18 cools. finch self-dispersion tests are conducted in the absence of an insoluble solvent.

When the 'hydrophile-hydrophobe balance is abovethe indicated minimumKZ moles of ethylene oxide per phenolic nucleus or'the equivalent) but insuincient to give a $01 as described immediately preceding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by having present 10% to 50% "of an inert solvent such as xylene. All that one need to do is tohave a xylene solution within the range of 59 to parts by weight of oxyalkalated derivatives and 50 to 10 parts by weight of xyleneand mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which maybe of the oil-in-water type or the water-ino il type" (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxya'lkylated" derivative. We prefer simply to use the xylene diluted derivatit es, which are described elsewhere, for this test rather than evaporate the solvent and employ anymore elaborate tests, if the solubility is not suiiicient to permit the simple sol test in water previously noted.

' If the product is not readily water soluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, -or diethylene glycol diethylether, with a little acetone added if required, making a rather concentrated solution, for instance 46% to 50%, and th'en'adding enough of the concentrated alcoholicor equivalent solution to give the previously sugg sted 9.5 to 5.0 strength solution. 'If the product is self -dispersing '(i. e., if the o'xyalkylated product is a liquid or a liquid solutionseli emulsifiable); such $01 or dispersion is referred to as at least semi-stable in the sense that sols, emulsions, or dispersions prepared are relatively stable,'if they remain at least for some period of tiriqefior instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 0.)". Needlessto say, a test can be made in the presence of an insoluble solvent such as 5% to 15% of xylene, as noted in previous examples. If such mixturai. e., containing a water-insolubl'e solvent; is at least semi-stable, obviously the solvent free product would be even more so. Surf ace activity representing an advanced hydrophilej hydrophobe balance can also be determined by the use'of conventional measurements hereinafter described. One outstanding characteristic property indicating surface-activity in a material is the ability to form a permanent foam in dilute aqueous solution, ior example, less than 0.5%,

when in"th e"higheroxyalkylated stage, and to form an emulsion in t'he lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation to the liydrophile properties'bf the final product. The principle involved in the manufacture of the here- 'inconteniplat'ed-compounds for use as polyhydric reactants, is ibased onthe'conversion of a hydrophbe'or non hydr'ophil"compound or mixture of compounds into products' which are distinctly hydrdphile, at least to the extent that they have emulsiiying properties 'or are self-emulsifying; :that is, when shaken with water they produce stable or sen'ii stablesuspensions, or, in the presenceoi a water-insoluble solvent, such as xylene, an emulsion. I'n demulsific'a'tion, it is sometimes preferable'to use apreq ct having markedly enhanced hydrophile properties over and above the tial stage'of self-em'ulsifiability, although We have found that with products of the type used herein, most efficacious results are obtained with products which do not have hydrophile properties beyond the stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against paraffin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably determined in this same manner but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an cil-in-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylenewater emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. Ihe emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4% units per resin mole cule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalentof xylene for the purpose of this test.

In many cases, there is no doubt as to the pres-' 20 ene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self -emulsification. For this reason if to emulsify an insoluble solvent such as xylene.v It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has "been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature or structure of the resin polymer obtained varies somewhat, with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc. 7

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating-step, contains 3 to 6 or 7 phenolic nuclei with approximately 4 /2 or 5 /2 nuclei as an average, More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable procedure, particularly by cryoscopic methods; but using the same reactants and using more drastic conditions of resinification one usually finds that higher molecular weights are indicated by higher melting points of the resins and a tendency to decreased solubility. See what has been said elsewhere herein in regard to a secondary step involving the heating of a resin with or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalyst is advantageously used in preparing the resin. A combination of catalysts is sometimes used in two stages; for instance, an alkaline catalyst is sometimes employed in a first stage, followed by neutralization and In other.

addition of a small amount of acid catalyst in-a second stage. It is generally believedthat even in the presence of analkaline catalyst, the-number of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol em.- ployed in order to introduce methylol groups'cin the intermediate stage. There is. no: indication that such groups appear in the finalresinif prepared by the use of an acid catalyst. It is possible that such groups may appear in the finished resins prepared solely with an alkaline catalyst; but we have never been able to confirm this fact in an examination of a large number of resins prepared by ourselves. Our preference, however, is to use an acid-catalyzed resin, particularly employing a formaldehyde-to-phenol ratio of 0.95 to 1120. and, as far as wehave been able to determine, such resins are free from methylol groups. As a matter of fact, it is probable that in acidcatalyzed resinifications, the methylol structure may appear only momentarily at the very beginning of the reaction and in all probability is converted at once into a more complex structure during the intermediate stage.

One procedure which can be employed inthe useof a new resin to prepare polyhydric reactants for use in the preparation of compounds employed in the present invention, is to determine the hydroxyl value by the Verley-Bdlsing method or its equivalent. The resin as such, or in the form of a solution as described, is then treated with ethylene oxide in presence of 0.5% to 2% of sodium methylate as a catalyst in stepwise fashion. The conditions of reaction, as far as time" or per cent are concerned, are within :5

the range previously indicated. With suitable agitation the ethylene oxide, if added in molecular proportion, combines within a comparatively short time, for instance a few minutes to 2 to 6 hours, but'in some instances requires as much as 8 to 24 hours. A useful'temperature range is from 125 to 225 C. The completion of the reaction of each addition of ethylene oxide in stepwise fashion is usually indicated by the reduction or elimination of pressure. An amount conveniently used for each addition is generally equivalent 'to a mole or two moles of ethylene oxide per hydroxyl radical. When'the amount of ethylene oxide added is equivalent to approximately by weight of the original resin, a sample is tested for incipient hydrophile properties by simply shaking up in water as is, orafter the elimination of the solvent if a solvent is present. The amount of ethylene oxide used to obtainauseful demulsifying agent as a rule varies from by weight of the original resin toas much as five or six times the weight of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more eifective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact thatin the subsequent examples reference is made to the stepwise addition of the alkylene' oxide, such as ethylene oxide. It is understood, of course, there .is no objection to the continuous addition'of alkylene oxide until the desired stage of reaction is reached. ,Infacttheremay beless of aha'zard .creasedtamounts of alkylene oxide. ..one doesnot. even care to go to the trouble of 22 involved and it is often advantageous to add the alkylene oxide slowly in a continuous stream and in such amount as toavoid exceeding the higher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at to C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and particularly oxyethylation. What has been said previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydric alcohols in a surface-active or sub-surface-active range without examining them by reaction with a number of the typical acids and hydroxylated high molal amines herein described and subsequently examining the resultant for utility, either in demulsification or in some other art or industry as referred to elsewhere, or as a reactant for the manufacture of more complicated derivatives. A few simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2 to l; 6 to l; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present, such as Xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacityto form an emulsion when admixed with xylene or other insoluble solvent. If neither test shows the required minimum hydrophile property, repetition using 2 /2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to l or 19 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed .in. a comparatively thin layer, for instance the parent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0 aqueous solution is shaken,

is .an excellent test for surface activity. Previous reference has been made to the fact that other .oxyalkylating agents may require the use of in- However, if

2 3.. calculating moleculanweights, one' can simply arbitrarily prepare compounds containing ethylene oxide equivalentto about 50% to 75% by weight, for example 65% by weight,- of the resin to be oxyethylated; a second example using approximately 200% to 300% by-w'eight, and a third example using about 500% to 750% by weight, to explore the range of hydrophile-hydrophobe balance.

i A practical examination of the factor of oxyalkylation level can be made by a very simple test using a pilot plant autoclave having a capacity of about to gallons as hereinafter described. Such laboratory-prepared routine compounds can then be tested for solubility and, generally speaking, this is all that isrequ-ired to give 'a suitable variety covering the hydrophile-hydro phobe range. All these tests, as Stated, are intended to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly arbitrary manner, a series or" compounds illustrating the hydrophilehydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (1?) the nature of the aldehydic residue, which is usually CH2; and (c) the nature of the substituent, which is usually butyl, amyl, or phenyl. With such information one is in substantially the same position as if one had personally made the resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units of the resin of the following over-simplified formula:

(n=1 to 13, or even more) is given approximately by the formula: (Mol. wt. of phenol 2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight 0f the resin would be 11. times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular Weight is given approximately by taking (11. plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculation will be in error by several percent; but as it grows larger, tocontain 6, 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight, one need only introduce, for example; two molal.

weights of ethylene oxide or slightly 'more, per phenolic nucleus, to produce aproduct of minimal hydrophile character. Further oxyalkylation gives enhanced "hydrophile character. A1-

though two have prepared and tested a large number'of oxyethylated products of the type describedherein, we have found no instance where the use of less than 2 moles of ethylene oxide per phenolic nucleus gave desirable products.-'

Examples 12) through 18b, and the tables which appear in columns 51 through 56 of our said Patent 2,499,370 illustrate oxyalkylation products from resins which are useful as intermediates; for. producing the quaternary ammonium compounds used in accordancewith the present application, such examples giving exact and complete details for carrying out the oxyalkylation procedure.

The resins,; prior to oxyalkylation, vary from tacky,viscous liquids to hard, high-melting solids. :Their color varies from a light yellow through amber, to a deep red or even almost black. In the manufacture of resins, particularly hard resins, as the reaction progresses the reaction mass frequently goes through a liquid state to a sub-resinous or semi-resinous state, often characterized by being tacky'or sticky, toja final complete resin. As the resin is subjected ,to oxyalkylation these same physical changes tend to take place in reverse. If one starts with a solid resin, oxyalkylation tends to make it tacky or semi-resinous and further oxyalkylation makes the tackiness disappear and changes the product to a liquid. Thus, as the resin is oxyalkylated it decreases in viscosity, that is, becomes more liquid or changes from a solid to a liquid, particularly when it is converted to the Water-dispersible or water-soluble stage. The color of the oxyalkylated derivative is usually considerably lighter than the original product from which it is made, varyin from a pale straw color to an amber or reddish amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick viscous sirup.

Some products are waxy. The presence of a solvent, such as 15% xylene or the like, thins the viscosity considerably and also reduces the color in dilution. No undue significance need 'beattached to the color for the reason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared as customarily employed in varnish resin manufacture, i. e., a procedure that excludes the presence of oxygen during the resinification and subsequent cooling of the resin, then of course the initial resin is much lighter in color. We have employed some resins which initially are almost water-white and also yield a lighter colored final product.

Actually, in considering the ratio of alkylene oxide to-add, and we have previously pointed out that this can be pre-determined using laboratory tests, it is our actual preference from a practical standpoint to make tests on a small pilot plant scale. Our reason for so doing is that we make one run, and only one, and that we have a complete series which shows the progressive effect of introducing the oxyalkylating-agent, for instance, the ethyleneoxy radicals. Our preferred procedure is as follows: We prepare a suitable resin, or for that matter, purchase it in the open market. We employ 8 pounds of resin and 4 pounds of xylene and place the resin and Xylene in a suitable autoclave with an open reflux condenser. We prefer to heat and stir until the solution is complete. We have pointed out that soft resins which are fluid or semi-fluid can be readily prepared in various ways, such as the use of ortho-tertiary' amylphenol, ortho-hydroxydiphenyl, ortho-decylphenol, or by the use of higher molecular weight aldehydes than formaldehyde. If such resins are used, a solvent need not be added but may be added as a matter of convenience or for comparison, if desired. W'e'then add a catalyst, for instance, 2% of caustic soda, in the form of a 20% to 30% solution, and remove the water of solution or formation. We then shut 01f the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin. We prefer a temperatureof about 150 C. to 175 C. We also take samples at intermediate points as indicated in the following table:

Pounds of Ethylene Percentages Oxide Added per S-pound Batch 66% 5. 33 75 6.0 100 8.0 150 12. o 200 16. O 300 24. 0 400 32.0 500 40. 0 600 4s. 9 750 60. 0

Oxyethylation to 750% can usually be completed within 30 hours and frequently more quickly.

The samples taken are rather small, for instance, 2 to 4 ounces, so .that no correction need be made in regard to the residual reaction mass. Each sample is divided in two. One-half the sample is placed in an evaporating dish on the steam bath overnight so as to eliminate the xylene. Then 1.5% solutionsare prepared from both series of samples, i. e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be suflicient to indicate hydrophile character or surface activity, i. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property. All these properties are related through adsorptionat the interface, for example, a gas-liquid interface or a liquid-liquid interface. If desired, surface activity can be measured in any one of the usual ways using a DuNouy tensiometer or dropping pipette, or any other procedure for measuring interfacial tension. Such tests are con ventional and require no further description. Any compound having sub-surface-activity,- and all derived from the same resin and oxyalkylated to a greater extent, .i. e., those having a greater proportion of alkylene oxide, are useful as polyhydric reactants for the practice of this invention. Another reason why we prefer to use a pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a laboratoryscale test which will indicate whether .or not a resin, although soluble insolvent, will yield an insoluble rubberyproduct, i. e., a product which is neither hydrophile nor surface-active, upon oxyethylation, particularly exlit tensive oxyethylation. It is also obvious that one may have a solvent-soluble resin derived from a mixture of phenols having present 1% to 2% of a trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addition of 2 or 3 moles of the oxyalkylating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-activereactant which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable reactant. It is obvious that this present procedure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its effect on solubilityand also thefact that, if carried far enough, it causes incipient stringiness, then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced stringiness, or even the tendency toward a rubbery stage, isnot objectionable so long as the final product is still hydrophile and at least sub-surface-active.

, Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point which we want to make here, however, is this: Stringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a difunctional phenol and an aldehyde produce a non-cross-linked resin molecule and if such molecule is oxyalkylated so as to introduce a plurality of hydroxyl groups in each molecule, then and in that event if subsequent etherification takes place, one is going to obtain crosslinking in the same general way that one would obtain cross-linking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethylene oxide. This may be done in a comparatively short time, for instance, at or C. in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or 5 times as long to introduce an equal amount of ethylene oxide employing the same temperature, then etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time period. 7

It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermo-plastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence ofsome accompanying water-insoluble solvent such as to of xylene. Further oxyalkylation, particularly oxyethylation, ma then yield a product which, instead of giving a clear solution as previously, gives a very milky solution suggesting that some marked change has taken place. One explanation of the above change is that'the structural unit indicated in the following way where 8n is a fairly large number, ,for instance, 10 to 20, decomposes andan oxyalkylate'd resin representing a lower degree of oxyethylation and a less soluble one, is generated and a cyclic polymer of ethylene oxide is produced, indicated thus:

I i BCH HCH noted. In'joxyalkylation, any-solventemployed should be non-reactive to the alkylene oxide employed; This limitation does not apply to solvents This fact, of course, presents no difiicultv for the reason that oxyalkvlation can be conducted in each instance step iseor at a gradual rate, and samples taken at short intervals so, as to arrive at a point where optimum surface activity or hydrophile character is obtained if desired; for

products for use as polyhydric reactants in the practice of this invention. this is not necessary and, in fact, may be undesirable, i. e., reduce the efficiency of the product.

We do not know to what extent oxyalkylation produces uni orm distr bution phenolic hydroxyls present in the resin molecule. In someinstances. of course, such distribution can not be uniform for the reason that we have,

not sp cified that the molecules of ethylene oxide, for example, be added in multi les of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happensto have five phenolic nuclei. If a minimum of two moles of ethylene oxide per phenolic nucleus are add d. this would mean an addition of 10 moles of ethylene oxide,

but suppose that one added ll moles' of ethylene oxide, or '12, or 13, or 14 moles: obviously, even assuming the most uniform distribution possible} some of the polyethyleneoxy radicals would con tain 3 ethyleneoxy units and some would con tain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent.

For that matter, if one were to introduce moles of ethylene oxide there is no way to be certain that all chains of ethyleneoxy units would have 5 units; there might be some having, for

example, e'and 6 units,- or for that matter 3 or '7, Nor is there any basis for assuming that derivatives of the latter, the following should be in regard to the oxyalkvlated compounds, and for that matter oxyalkylating agent, 7

as alcohols, ether alcohols, c'resols, phenols, ketones, esters, etc.-,'alone or with the addition of water. Some of th'ese are mentioned hereafter. We prefer the use of benzene or diphenylamine as a solvent in making cryoscopic' (measurements. The most satisfactory resins are those which are soluble in xylene 'or the like, rather than those which are soluble only in some other solvent containing elements other than carbon and hydrogen,for instance, oxygen or chlorine. Such solvents are usually polar, semi-polar, or slightly polar in nature compared with xylene, cymene, etc.

Reference: :tocryoscopic measurement is con. cerned with the use of benzene or other suitable compound as a solvent. Such method will show that conventional resins obtained, for example. from para-tertiary amylphenol and formaldehyde in presence of an acid catalyst, will have a molecular weight indicating 3, 4, 5 or somewhat greater number ofstructural units per molecule. If more drastic conditions of resinification are employed or if such low-stage resin'is subjected to" a vacuum distillation treatment as previously described, one obtains a resin of a distinctly higher molecular weight. Any molecular weight determination used, whether cryoscopic measurement or otherwise, other than the conventional cryoscopic one employing benzene, should be checked so as'to insure that it gives consistent values on such conventional resins as a control. quently all that is necessary to make an approximation of the molecular weight range is to make a comparison with the dimer obtained by chemi-- cal combination of two moles of thesame phenol,

and one mole' of the same aldehyde under con-' ditions to insure dimerization. As to the pre-' paration of such dimers'from substituted phenols,-

The in-' see 'Carswell, Phenoplasts, page 31. creased viscosity. resinous character, and decreased solubility, etc., of'the higher polymers in comparison with the dimer, frequently are all that is required to establish that the resin contains 3- or more structural units per molecule.

Ordinarly the oxyalkylation iscarried out in, autoclaves provided with agitators or stirring devices. We have found that the speed of the agita- In some cases, the change from slowspeed agita.. tion, for examplain a laboratory autoc lave ,agitation; markedly influences the reaction time.

Fre-" tion with a stirrer operating at aspeed of 60 to- 200 R. P. M., to high speed agitation, with the stirrer operating at 250 to 350 R. P. M., reduces the time required for oxyalkylation by about onehalf to two-thirds. Frequently xylene-soluble products which give insoluble products by procedures employing comparatively slow speed agitatiomgive suitable hydrophil'e products when produced by similar procedure but with high speed agitation, as a result, we believe, of the reduction in the time required with consequent elimination or curtailment of opportunity for curing or etherization. Even if the formation of an insoluble product is not involved, it is frequently advantageeusto speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale operations, we have'demonstrated that economical manufacturing results from continuous oxyalkylation, that is, an operation in which the alkylene oxide is continuously fed to the reaction vessel, with high speed agitation, i. e., an. agitator operating at 256 to 350 R. P. M. Continuous oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordinarily more' convenient for laboratory operation.

Previous reference has been made to the fact that in preparing compounds of the kind herein described, particularly adapted fordemulsification of water-in oil emulsions, and for that matter for other purposes, one should make a complete exploration of the wide variation in hydro phobe-hyd'rophile balance as previously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance of the oxyalkylated resins is imparted, as far as the range of variation goes, to a greater or lesser extent to the herein described derivatives. This means that one employing the present invention should take the choice of the most suitable derivative selected from a number of representative compounds,.thus,. not only should a variety'of resins be prepared exhibiting a variety of oxyal'kylations, particularly oxyethylations, but also a variety of derivatives. This can be done convene iently in light of what has been said previously. From a practical standpoint, using pilot plant equipment, for instance, an autoclave having a capacity of approximately three to five gallons. We have made a single run by appropriate selections in which the molal ratio of resin equivalent to ethylene oxide is 1 to 1, 1 to 5, 1 tell), 1 to 15, and 1 to 20. Furthermore, in making these particular runs we have used continuous addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided that the pressure of the ethylene oxide was sulTciently great to pass into the autoclave, or else we have used-.ian arrangement which, in essence, was the equivalent of an ethylene oxide cylinder with a means for injecting nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with the means for either weighing the cylinder or measuring the ethylene oxide used' volumetrically. Such procedure and arrangement for injecting liquids is, of course, conventional. The following data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five diiferent variants in oxyethylation. In.

adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediresins on laboratory scale are described.

30 ately' if there is any indication that reaction is stopped or, obviously, if reaction is not started at the beginning of the reaction period. Since the addition of ethylene oxide is invariably an exothermic reaction, whether or not reaction has taken place can be judged in the usual manner by observing (a) temperature rise or drop, if any, (2)) amount of cooling water or other means required to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling water or equivalent, or if there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately following, we are showing the maximum temperature which is usually the operating temperature. In other words, by experience we have found that if the initial reactants are raised to the indicated temperature and then if ethylene oxide is added slowly, this temperature is maintained by cooling water until the oxyethylation is complete- We ,have' also indicated the maximum pressure that we obtained or the pressure range. Likewise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxy ethylation period. As one period ends it will be noted we have removed part of the oxyethyl'ated mass to give us derivatives, as therein described; the rest has been subjected to further treatment. All this is apparent by examining the columns headed Starting mix, Mix at end of reaction, Mix which is removed for sample, and "Mix which remains as next starter.

The resins employed are prepared in the manner described in Examples 1a through 103a of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were prepared in 10 to 15-gallon electro-vapor heated synthetic resin pilot plant reactors, as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and completely described in their bulletin No. 2087 issued in 1947, with specific reference to specification No. 71-3965.

For convenience, the following tables give the numbers of the examples of our said Patent 2,499,370 in which the preparation of identical It is understood that in the following examples, the change is one with respect to the size of the operation.

The solvent used in each instance was xylene. This solvent is particularly satisfactory for the reason that it can be removed readily by distillation or vacuum distillation. In these continuous experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, /2 to one gallon, one can proceed through the entire molal stage of 1 to 1, to 1 to 20, without remaking at any intermediate stage. This is illustrated by Example 10412. In other examples we found it desirable to take a larger sample, for instance, a 3-gallon sample, at an intermediate stage. As a 'result it was necessary in such instances to start Phenol for resin: Para-tertiary"amylphenol 1 Aldehyde for resin: Formaldehyde Date, one '22,: 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 3a of Patent 2,499,370 but this batch designated 104a.) I.

. Mix Which is Mix Which Re- Starting Mix figg figg of Removed for mains as Next Sample Starter Max. Max. Time Pressure, Tempera Solubility lbs.sq. in.. ture, C. lbls. abs. Lbs Ifibs. Lbs Ifibs. Lbq gbs. Lbs o eseso eso esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Reinto EtO Molal Ratio 1:1 14.25 15.75 0 14. 15.75 4.0 3.35 3.65 1.0 10.9 12.1 3.0 80 150 ,4 I Ex. No. 104b Second Stage Resin to EtO V Molal Ratio 1:5 10 9 12.1 3.0 10.9 12.1 15.25 3. 77 4.17 5. 31 7.13 7.93 9. 94 158 ,6 ST Ex. No.105b

Third Stage Resin to EtO Molal Ratio 1:10. 7 13 7.93 9.94 7.13 7. 93 19. 69 3. 29 3. 68 9.04 3.84 4.25 10.65 60 173 M; FS Ex. No. 10Gb--."

Fourth Stage Resinto EtO s Molal Ratio 1:15. 3.84 4. 25 10.65 3.84 4. 25 16.15 2.04 2.21 8.55 1.80 2.04 7.60 220 160 36 RS Ex. No. 107b Fifth Stage Resin to 1310;.-. Molal Ratio 1:20 1. 2.04 7.60 1.80 2. 04 10.2 V3 QS Ex. No.108b

I=l'.nsoluble. ST =Slight tendency toward becoming soluble. FS=Fairly soluble. RS=Readi1y soluble. QS=Quite soluble.

Phenol for resin: Nonylphenol Aldehyde for resin: Formaldehyde Date, .1 one 18. 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 70a of Patent 2,499,370 but this batch designated 10911.]

Mix Which is Mix Which Re- Starting Mix igg ggg of Removed for mains as Next Sample Starter Max Max P1 assure, Tempera- Time Solubility Lbs Lbs Lb Lbs Lbs Lb Lbs Lbs Lb Lbs Lbs Lb Sol- Res Sol Res Sol Res Sol Res vent in Eto vent in Eto vent in Eto vent in Etu First Stage Resin to EtO- M01211 Ratio 1:1- 15 0 15. 0 0 15. 0 15. 0 3 5. 0 5. 0 1. 0 10. 0 10. 0 2. 0 50 150 1% ST EX. N0. 109b.

Second Stage Resin to Et0 Molal Ratio 1:5" 10 10 2 0 10 10 9 4 2 72 2 72 2.56 7 27 7 27 6 86 100 147 2 DT Ex. No.110b.

Third Stage Resin to EtO.. I M0131 Ratio 1:10. 7 27 7. 27 6. 86 7. 27 7. 27 13. 7 4. 16 4. 16 7. 68 3. 15 3. 15 5. 95 125 1% S Ex. N0. 111b Fourth Stage Resin to EtO. M01211 Ratio 1:15. 3 15 3. 15 5.95 3.15 3.15 8.05 1.05 1.05 2.95 2.10 2.10 6.00 220 174 2% S Ex. NO. 1120-.--..

Fifth Stage Resinto EtO 'Molal Ratio 1:20- 2.10 2.10 6. 00 2. 10 2.10 8.00 220 183 $1; VS

Ex. No. 113b V S Soluble. ST Slight tendency toward solubility. D T Definite tendency toward solubility. VS Very soluble.

ammo PhmotfarmaimrParmoctylphenoi Aldehgdojor rosin: Formaldehyde.

Date, June 23, 24, 1948 [Resin made" in. pilot plantsizei hatch. approximately 25 pounds, corresponding-to Bani Pamzwnambut, this-batch designated- 114a.)

1 Mix Whirlris I Mix Which. Re- Starting Mix gi g figg Removed r: -malns New r v I Sample; Starter V Max. Max. Time I Pressure, 'Iempgra- Solubility Ib s. 155; *gb sw I bs. Lbs 1 .11 5. abs. Lgxs. an m 0.- es 0- es- 0- ,QS. esvent in E vents in Em vent in Em want: in

First Stage,

Resin to EtO. I l Molai Ratio 1: 14:2 15.8 0. 14.2 "15.811; 3125 '5 3.15 3.4 0. 7511.1 112.4 2;.5 50 1601: 1%: NBI- Ex.No.114b Y 1 Second Stage }11.1. 12.4 .2.5 11.1-12,4 '1215 *f 7.05. 7.152. 2,887. 4.1 4158? 4.62' 100 171 iii 5 33 Third Stage Resin to EtO j. Molal Ratio 5&6! 7. 36 J 6.64- 7.36.154). V 120 190 1% S Ex.No.116h. g

Fourth Stage Rosin to m0 1 f Molal Ratio 1: 4.40 4. 9 (13; 4.4 4. 9. 1.4.8; j 400 '1 160 H V5 Ex. No.117b r 1 Fifth Stage Resin to EtO Molal R'at-io 1:20. 4.21. 4. 58 4'; 62 4.1 4.5 18. 3 260 172 16 VS! Ex. No. 118b.

S Soluble. NS =Not soluble. SS Somewhat soluble. VSYBIYQOIQDIB;

Pfimaljforrasim Menthylphemzl Aldehyde-forum; Formaldehyde Date, July 813, 1948 [Resin madam-pilot plant sizezbatnhmppmximatelyifi'pounds; corresponding to 69;: u! PatenbZAQQfi'm but thio batch designated lwml Mix Which 13. Mix Which Re- Starting Mix figi ggg Removezdior mains'as'Nextf a Sample. Starter Max Max Time 4 V V Pressure, Tempgrw mt Solubility l'bls. Ebs. Lbs Isiblsu abs. Lbs 1 2 115.. Lbs .ISzbls; gm. Lbs

o es- 0- es- 1 es-- n- .eS- l vent in Eto vent. in Eto went in Em went in to First Stage Resin to EtO. V Moi-ti Ratio 1: }l3.65 16.35 01 13.65 :16. 310 9;552.11; I 2. 1 4.1. 4.91 0.9 1% NS: EX. N0. 1190..

Second Stage Resinto EtO- I Molal Ratio-1:51. 10" 12 0 10 12 111755 4252 '5.42-f4.81 -'5.48 6;58-' 5;94i:. 140 1%, S= Ex. No; 1'20b I Third Stage Resinto E1;0 l M0151 Ratio"1:l0-}5 48 6.58 15.194 5.48 .nssoass l 9 0 1i 8 Ex. N0. 1211;"-.. A

Fourth Stage Resin to nt0 I H M0125] Ratio-1315- 4J1 4.9' 059 4.1 l 429 $131 18D 171 Hi2 Ex. N0. 122b....

Filth Stage Resin to EtQl... Moiai R3tirr120-}3i 10 3.72 .0. 68 3. l0. 3..72..l3..43 $20 1 0 Ex. No. 12317..-"

S Soluble. N S=N 0t soluble. VS =Very soluble.

Phenalfof 'resm.-= Pard-seco'ndafiyg baty'lphenal 'Aldehyde'jfor iesin: 'Fbrma'ldehyde Date, July 14-15, 1948 [Resinmad iii-iaiidt 'plant size-hawk; eliproiziiuetely pbuiids, corresponding to 2a of Patent 2,499,370 but thisb a'tch design'ted 12411.]

. 7 Mix Which is I Mix Whifih Restarting Mi! figg figg' Removed for mains as Next Sample Starter Max V Pressure, Temp era- Solubility 1 .11 5. Ifibs. Islbls. Ifibs. B l b s. llbs. lslbls. abs. Lbs

0 es- 0 es- 0 eso esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin te Eton..- 4 I v v n 1' H MolaiRatio 1: 14.45 15. 55 O 14. 15. 4. 25 5. 97 6. 38 '1. 8. 48 9. 17 2. 50 I 60 I 150 772 NS Ex. No.124b- N Second Stag/e Resin,t Et0 p l v M0181 Ratio 1 8:48 9.17 2-50 8.48 9.17 1610 5. 83 (132 11.05 2.65 2.85 4. l I 95 .1 188: )5 l SS Ex. No.125b. I g 7 Third Staa 82 5.18 6 4.82 5.18 14.25----- I 40o 183- S i g 1 I s }3i8s 4.15 To 3.85- mat 1-7.0 f 180 'l 1%! vs Ex. N0. 127b.

' 1 j i i Fifth Stage: i f

1 I 7 Resinta FtO.' i s v I V MOIZI 'RBtiO 1 2.65 2.85 4.95 2.65 3.85 1.5;45- 8D I 170 9i: VS Ex. No. 1281: 4

S Soluble. NS =Not soluble. SS Somewhat sblniile. VS =Very soluble.

Date, August 12-13, 1948 [Resin made 'on pilot plant size butch, approximately 25 poundsfcorresponding to 81a of Patent 2,499,370 but this batch designated 129a.)

1 T Mix Whibhis Mix Which Re- Starting Mix igs figg' Removed'for mains as Next Sample Starter Max. Max., Time Pressure, Tempgrahm Solubility gbls. abs. Lbs 'Ibls. gas. B Lsblslibs. gbls. Ibs. Lbs 1 0 eso es- 0 eso esvent in Eto vent in Eto vent in Ei went in Eto First Stage Resin to. Etoj v M0181 Ratio 1 12.8 2. 75 4. 25 57 0.95 8.55 11.50 1.80 110 150 $6 N01; soluble. Ex. No. 129b 1 Second Stag}: v Resin to Etoim- V T 1 1 a 1 Molal Ratio 1;5 8' 55 9. 3; '1. 78 6. 42 5. 2. 3. 77 5.08 4. 10 100 170 Somewhat Ex. No. 130b I 1 soluble.

Third sta e; f Resin to no..." i i 1 M0131 Ratio 1:10. 3 77 5. 08 -4. 10 3.77 5.08 13.-1 100 182 3 Ha Soluble. Ex. No. 131b 1 I Fourth Stage Resinto EtO v i t a Molal' Ratio 1:15. 5 2 7.0 5.2 ---7.0 47.0 340 17 10.13 2.10 4 2.83 6.87 r 200 .i 182 34 7617501111710. Ex. No.'132b j i Fifth Stage? Resin to Et0. Q 1 r v Molal Ratio 1:20. 2.10 2. 83 6.87 2.10 2.83 -9. 3 T 90 .96 Verysoluble. EX. No. 1330 v Phenol for resin: Pe'ra-tertim-y amylphenol Aldehyde for resin: Fnrfural Date, August 27-31, 1948 [Resin made on pilot plant size batch, anoroximately 25 pounds, corresponding to 42a of Patent 2,499,370 but this batch designated as 13411.]

. Which is Mix Which Re- Starting Mix fi 'g ggg of Removed for mains asNext Sample Starter Max. Max. Time Pressure, Temp era- Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

Sol- Res- Sol- Res- Sol- Res- Sol- Resvent in vent in vent in vent in First Stage Resin to EtO Mo1a1 Ratio 1:1 11 2 18.0 11.2 18.0 3.5 2.75 4.4 0.85 8.45 13. 6 i 2.65 120 135 $9 Not 501111718- Ex. No. 134b Second Stage Resin to Et Molal Ratio 1:5 8 45 13.6 .2. 65 8.45 13.6 12.65 5.03 8.12 7.55 3. 42 5. 48 5.10 110 150 }4 Somewhat Ex.v No. 13512----" soluble;

Third Stage.

Resin to EtO.. 1 I i Molal Ratio 1:10.. 4-5 8.0 L 4. 8.0 14.5 2.45 4.35 7.99 2.05 3.65 6.60 180 163 M Soluble.- Ex. No.136b

Fourth Stage 7 Resin to I i t0.-- Molal Ratio l 3.42 5.48 5.10 3.42 5.48 15.10 s 180 188 My Verysoluble. Ex. No; 13711.

Fifth Stage Resin to EtO.; 1 Molal Ratio1:20 2 05 3.65 6. 60 2.05 3.65 13.35 120 125 $6 Vel'YSolllblB. Ex. No. 1386.--."

Phenol for resin: Menihyl Aldehyde for resin: Fnrfural Date, Sept. 23-24, 1948 [Resiumade on pilot size batch, approximately 25 pounds, corresponding to 890 of Patent 2,499.370 but this batch designated as 139a.]

Mix Which is Mix W'hich Re- Starting Mix E of Removed for mains as Next G on Sample Starter Max Max V gressuie, Tgge, Solubility Lbs; Lbs. Lbs. Lbs Lbs. Lbs. Lbs. Lbs.

Lbs. Lbs. Lbs. Lbs. Sol- Res Soi- Res- 801- Res 801- Resvent in Eto vent in vent in- Eto vent in Eto First Stage Y Resin to EtO. I Molal Ratio 1:1- 10. 25 17. 75 10.25 17. 75 2. 5 2. 65 4. 0. 7. 6 13. 15 1. 150 }6 Not soluble. Ex. No-139b 1 v Second Stage Resin to EtO I Molal Ratio 1:5..- 7 6 13. 15 1. 85 7.6 13. 15 9. 35 5. 2 9. 00 6. 40 2. 4 4. 15 2. 80 177 }6 Somewhat Ex; No. 1140b-...-.. i soluble.

Thirdsmge Resin to EtO i s Molal Ratio 1:10-. 4. 22 6. 98 i 4. 22 6. 98 10. 0 90 i 165 M Soluble. Ex..No. 141b 1 Fourth Stage Resin to Eto 1 Molal Ratio 1:15.- 3 76 6. 24 3. 76 6. 24 18.25 171 $4 Very soluble. Ex. Ala-14212.--.

Fifth S tage'.

Resin to EtO. Molal Raiio1:20. 2 4 4.15 2. 95 2.4 4.15 11.70 90 $6 Verysoluble. Ex. N o. 143b.-..

Date, October 7-8, 1948 [Resin made on pilot plant size batch, approximately 25 pounds, corresponding to 42a of Patent 2,499,370 with 206 parts by weight of commercial para-oetylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 14411.]

- Mix Whichis Mix Which Re- Starting Mix igg figg of Removed for mains as Next Sample Starter 1 Max. Max. Time Pressure Temlgerahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. we

Sol- Res- Sol- Res- Sol- Res- S Resvent in vent in vent in vent in First Stage Resin to EtO Molal Ratio 1:1.. 12.1 18. 6 12. 1 18. 6 3. 0 5. 38 8.28 1. 34 6. 72 10. 32 1. 66 80 150 M2 Insoluble. Ex. No. 1446..-

Second Stage Slight tend- Resinto Et0 ency t0- Molal Ratio 1:5 9. 14.25 9. 25 14. 25 11.0 3. 73 5.73 4. 44 5. 52 8.52 6. 56 100 177 942 Ward be- Ex. No. 1456..... coming soluble. Third Stage Resin to EtO Molal Ratio 1:10. 6. 72 10.32 1. 66 6. 72 10.32 14.91 4. 97 7. 62 11.01 1. 75 2. 70 3. 90 182 1 Fairly solu- Ex. No. 146b....- ble.

Fourth Stage Resin to EtO- Molal Ratio 1:15- 5. 52 8.52 6. 56 5. 52 8. 52 19. 81 100 176 M; Readily sol- Ex. No. 147b.. uble.

Fifth Stage Resin to EtO Molal Ratio 1:20. 1. 75 2. 70 3. 1. 75 2. 70 8. 4 80 160 $4 Quite solu- Ex. No. 1481). ble.

Date, October 11-13, 1948 [Resin made on pilot plant size batch, approximately 25 pounds, corresp paraphenylphenol replacing 164 parts by welght of para.-

Phenol f5; resi m P ara p henyl Aldehyde for resin: Farfaral onding to 42a of Patent 2,499,370 with 170 parts by weight of cornmercial tertiary amylphenol but this batch designated as 14911.]

Mix Which is Mix Which Re- Starting Mix g figg of Removed for mains as Next Sample Starter Max Max Time llljressure '{emgeaahrs Solubility s. sq. in. are s25: 123: {@133 s21: {12:1 5 s: 1222: Ei: i123: g ggvent in vent in vent in vent in First Stage Resin to EtO Molal Ratio 121.. 13.9 16.7 13.9 16.7 3.0 3.50 4.25 0.80 10.35 12.45 2.20 $6 Insoluble. Ex. No. 1496"..-

Second Stage Resin to momsliggt Molal Ratio 1:5... 10.35 12.45 2.20 10.35 12.45 12.20 5.15 0.19 6.06 5.20 6.26 0.14 so 183 y, e Ex 110.1500".-.

- billty.

Third Stage Resin to EtO. Molal Ratio 1:10. 8.90 10.7 8.90 10.70 19.0 5.30 6.38 11.32 3.60 4.32 7.68 90 193 Z42 Fairly solu- Ex;No.151b ble.

' Fourth Stage Resin to EtO I I Molal Ratio 1:15. 5.20 6.26 6.14 5.20 6. 26 16.64 100 171 '%'Readily sol- Ex. No. 152b. uble.

Fifth Stage Resinto EtO.. Molal Ratio 1:20. 3.60 4.32 7.68 3.60 4.32 15.68 Samplesomewhat rubbery and gelat- 230 2 Ex. No. 1530..... inous but fairly soluble 

1. A PROCESS FOR BREAKING PETROLEUM EMULSION OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFLER INCLUDING A HYDROPHILE QUARTERNARY AMMONIUM COMPOUND OBTAINED BY REACTION BETWEEN A HYDROXYLATED HIGH MOLAL AMINE SELECTED FROM THE CLASS CONSISTING OF 